Unsaturated Reactive Intermediates and Related Chemistry

这项有机和高分子化学方面的拨款为犹他州大学的Peter Stang博士的研究提供了支持。这项工作的重点是准备和了解有机化学中不寻常的成键物种。对这些物种的综合利用也将进行研究。将考察三个独立的领域：a)不饱和卡宾，b)有机金属化学和c)应变环系。我们将研究硅作为手性助剂与亚烷基卡宾-叶立德的用途。金属介导的不饱和交叉偶联的详细机制将以铂为金属，三氟乙烯为底物进行研究。还将探讨不同的有机金属亲核剂与三氟代炔基乙烯基盐的相互作用。随着新的应变环体系的制备，新的亚烷基环丙烷的化学将得到发展，重点是氧化、环加成和金属络合物。动力学、立体化学、结构-反应性、核磁共振和X射线结构测定将是主要的技术和工具。虽然这些研究主要是基础性的，但它们将为合成有用的反应的详细机制提供相当大的洞察力。它们还将提供对有机金属途径的更好的理解，在这些途径中，基本的机械洞察力目前是有限的，并且非常需要。

This grant in Organic and Macromolecular Chemistry provides support for the research of Dr. Peter Stang, University of Utah. The work is focused on preparing and understanding unusual bonding species in organic chemistry. The synthetic use of such species also will be studied. Three independent areas will be examined: a) unsaturated carbenes, b) organometallic chemistry and c) strained ring systems. The uses of silicon as a chiral auxiliary along with alkylidenecarbene-ylides will be studied. The detailed mechanism of metal-mediated unsaturated cross couplings will be examined using Pt as the metal and vinyl triflates as the substrates. The interaction of varied organometallic nucleophiles with alkynylvinyl triflates will also be probed. The chemistry of the new alkylidencycloproparenes with emphasis on oxidation, cycloadditions, and metal complexes will be developed along with the preparation of new, novel strained ring systems. Kinetics, stereochemistry, structure-reactivity, NMR, and X-ray structure determinations will be the major techniques and tools employed. Although these studies are primarily of a fundamental nature, they will provide considerable insight into the detailed mechanism of synthetically useful reactions. They will also provide a better understanding of organometallic pathways where fundamental mechanistic insights are currently limited and greatly needed.